CA1310467C - Amelioration d'un procede direct au moyen du controle de la production du silicone - Google Patents

Amelioration d'un procede direct au moyen du controle de la production du silicone

Info

Publication number: CA1310467C
Authority: CA; Canada
Prior art keywords: silicon; phosphorus; phosphide; refining; compounds
Prior art date: 1986-12-22
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired - Lifetime

Application number

CA000552215A

Other languages

English (en)

Inventor

Roland L. Halm

Oliver K. Wilding, Jr.

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Dow Silicones Corp

Original Assignee

Dow Corning Corp

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1986-12-22

Filing date

1987-11-19

Publication date

1992-11-24

Family has litigation

First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25481183&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CA1310467(C) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.

1987-11-19 Application filed by Dow Corning Corp filed Critical Dow Corning Corp

1987-12-28 Priority to IN932/MAS/87A priority Critical patent/IN170526B/en

1992-11-24 Application granted granted Critical

1992-11-24 Publication of CA1310467C publication Critical patent/CA1310467C/fr

2009-11-24 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

229910052710 silicon Inorganic materials 0.000 title claims abstract description 82
239000010703 silicon Substances 0.000 title claims abstract description 81
XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
238000000034 method Methods 0.000 title claims abstract description 65
238000004519 manufacturing process Methods 0.000 title claims abstract description 11
238000007670 refining Methods 0.000 claims abstract description 22
150000003018 phosphorus compounds Chemical class 0.000 claims abstract description 12
OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 34
239000011574 phosphorus Substances 0.000 claims description 32
229910052698 phosphorus Inorganic materials 0.000 claims description 32
FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
150000001875 compounds Chemical class 0.000 claims description 16
238000006243 chemical reaction Methods 0.000 claims description 14
229910052802 copper Inorganic materials 0.000 claims description 11
239000010949 copper Substances 0.000 claims description 11
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
239000011780 sodium chloride Substances 0.000 claims description 10
238000002347 injection Methods 0.000 claims description 7
239000007924 injection Substances 0.000 claims description 7
ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
229910052718 tin Inorganic materials 0.000 claims description 5
XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
150000003606 tin compounds Chemical class 0.000 claims description 4
239000005749 Copper compound Substances 0.000 claims description 3
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
150000001350 alkyl halides Chemical class 0.000 claims description 3
150000001880 copper compounds Chemical class 0.000 claims description 3
-1 phosphorus compound Chemical class 0.000 claims description 3
229910052725 zinc Inorganic materials 0.000 claims description 3
239000011701 zinc Substances 0.000 claims description 3
IHGSAQHSAGRWNI-UHFFFAOYSA-N 1-(4-bromophenyl)-2,2,2-trifluoroethanone Chemical compound FC(F)(F)C(=O)C1=CC=C(Br)C=C1 IHGSAQHSAGRWNI-UHFFFAOYSA-N 0.000 claims description 2
PGYDGBCATBINCB-UHFFFAOYSA-N 4-diethoxyphosphoryl-n,n-dimethylaniline Chemical group CCOP(=O)(OCC)C1=CC=C(N(C)C)C=C1 PGYDGBCATBINCB-UHFFFAOYSA-N 0.000 claims description 2
239000006009 Calcium phosphide Substances 0.000 claims description 2
229910052786 argon Inorganic materials 0.000 claims description 2
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical group P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 2
239000001301 oxygen Substances 0.000 claims description 2
229910052760 oxygen Inorganic materials 0.000 claims description 2
150000003752 zinc compounds Chemical class 0.000 claims description 2
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
239000001506 calcium phosphate Substances 0.000 claims 1
239000000460 chlorine Substances 0.000 claims 1
229910052801 chlorine Inorganic materials 0.000 claims 1
229910052757 nitrogen Inorganic materials 0.000 claims 1
QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims 1
229940078499 tricalcium phosphate Drugs 0.000 claims 1
229910000391 tricalcium phosphate Inorganic materials 0.000 claims 1
235000019731 tricalcium phosphate Nutrition 0.000 claims 1
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
229910045601 alloy Inorganic materials 0.000 description 8
239000000956 alloy Substances 0.000 description 8
239000007789 gas Substances 0.000 description 8
238000007792 addition Methods 0.000 description 7
239000000654 additive Substances 0.000 description 7
235000012239 silicon dioxide Nutrition 0.000 description 7
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
230000000694 effects Effects 0.000 description 6
239000000377 silicon dioxide Substances 0.000 description 6
230000000996 additive effect Effects 0.000 description 5
239000000463 material Substances 0.000 description 5
239000000203 mixture Substances 0.000 description 5
239000000843 powder Substances 0.000 description 5
230000009257 reactivity Effects 0.000 description 5
229910000881 Cu alloy Inorganic materials 0.000 description 4
241000209094 Oryza Species 0.000 description 4
235000007164 Oryza sativa Nutrition 0.000 description 4
229910052751 metal Inorganic materials 0.000 description 4
239000002184 metal Substances 0.000 description 4
235000009566 rice Nutrition 0.000 description 4
239000004576 sand Substances 0.000 description 4
CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
235000011089 carbon dioxide Nutrition 0.000 description 3
239000003638 chemical reducing agent Substances 0.000 description 3
WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 3
229910052742 iron Inorganic materials 0.000 description 3
238000002844 melting Methods 0.000 description 3
230000008018 melting Effects 0.000 description 3
229940050176 methyl chloride Drugs 0.000 description 3
239000000376 reactant Substances 0.000 description 3
239000007787 solid Substances 0.000 description 3
239000011135 tin Substances 0.000 description 3
KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
DTAFLBZLAZYRDX-UHFFFAOYSA-N OOOOOO Chemical compound OOOOOO DTAFLBZLAZYRDX-UHFFFAOYSA-N 0.000 description 2
229910052782 aluminium Inorganic materials 0.000 description 2
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
230000009286 beneficial effect Effects 0.000 description 2
230000003197 catalytic effect Effects 0.000 description 2
239000003153 chemical reaction reagent Substances 0.000 description 2
NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
238000001816 cooling Methods 0.000 description 2
230000002939 deleterious effect Effects 0.000 description 2
239000008187 granular material Substances 0.000 description 2
239000002994 raw material Substances 0.000 description 2
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
KUGRPPRAQNPSQD-UHFFFAOYSA-N OOOOO Chemical compound OOOOO KUGRPPRAQNPSQD-UHFFFAOYSA-N 0.000 description 1
229910001096 P alloy Inorganic materials 0.000 description 1
229910000676 Si alloy Inorganic materials 0.000 description 1
238000003723 Smelting Methods 0.000 description 1
RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
229910052787 antimony Inorganic materials 0.000 description 1
WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
229910052785 arsenic Inorganic materials 0.000 description 1
RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
229910052797 bismuth Inorganic materials 0.000 description 1
JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
229910052793 cadmium Inorganic materials 0.000 description 1
BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
229910052799 carbon Inorganic materials 0.000 description 1
239000003575 carbonaceous material Substances 0.000 description 1
239000003054 catalyst Substances 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
239000003245 coal Substances 0.000 description 1
229910017052 cobalt Inorganic materials 0.000 description 1
239000010941 cobalt Substances 0.000 description 1
GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
239000000571 coke Substances 0.000 description 1
239000000356 contaminant Substances 0.000 description 1
150000001879 copper Chemical class 0.000 description 1
238000010891 electric arc Methods 0.000 description 1
230000002708 enhancing effect Effects 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
235000013312 flour Nutrition 0.000 description 1
238000005243 fluidization Methods 0.000 description 1
239000003517 fume Substances 0.000 description 1
229910052733 gallium Inorganic materials 0.000 description 1
238000004817 gas chromatography Methods 0.000 description 1
230000005484 gravity Effects 0.000 description 1
238000000227 grinding Methods 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
239000012535 impurity Substances 0.000 description 1
229910052738 indium Inorganic materials 0.000 description 1
APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
230000006698 induction Effects 0.000 description 1
239000004615 ingredient Substances 0.000 description 1
230000014759 maintenance of location Effects 0.000 description 1
150000002739 metals Chemical class 0.000 description 1
239000011812 mixed powder Substances 0.000 description 1
229910052759 nickel Inorganic materials 0.000 description 1
239000008188 pellet Substances 0.000 description 1
230000000737 periodic effect Effects 0.000 description 1
239000002574 poison Substances 0.000 description 1
231100000614 poison Toxicity 0.000 description 1
239000010453 quartz Substances 0.000 description 1
239000011541 reaction mixture Substances 0.000 description 1
238000011084 recovery Methods 0.000 description 1
238000010079 rubber tapping Methods 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
229910000077 silane Inorganic materials 0.000 description 1
230000002226 simultaneous effect Effects 0.000 description 1
238000005245 sintering Methods 0.000 description 1
229910052716 thallium Inorganic materials 0.000 description 1
BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
239000002023 wood Substances 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Silicon Compounds (AREA)
Catalysts (AREA)
Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

CA000552215A 1986-12-22 1987-11-19 Amelioration d'un procede direct au moyen du controle de la production du silicone Expired - Lifetime CA1310467C (fr)

Priority Applications (1)

Application Number	Priority Date	Filing Date	Title
IN932/MAS/87A IN170526B (fr)	1986-12-22	1987-12-28

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
US06/944,317 US4946978A (en)	1986-12-22	1986-12-22	Method of direct process performance improvement via control of silicon manufacture
US944,317		1986-12-22

Publications (1)

Publication Number	Publication Date
CA1310467C true CA1310467C (fr)	1992-11-24

Family

ID=25481183

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
CA000552215A Expired - Lifetime CA1310467C (fr)	1986-12-22	1987-11-19	Amelioration d'un procede direct au moyen du controle de la production du silicone

Country Status (8)

Country	Link
US (1)	US4946978A (fr)
EP (1)	EP0273635B2 (fr)
JP (1)	JP2543920B2 (fr)
CN (1)	CN1014506B (fr)
AU (1)	AU596480B2 (fr)
BR (1)	BR8706946A (fr)
CA (1)	CA1310467C (fr)
DE (1)	DE3784151T3 (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4898960A (en) *	1986-12-22	1990-02-06	Dow Corning Corporation	Method of direct process performance improvement via control of silicon manufacture
US5059343A (en) *	1986-12-22	1991-10-22	Dow Corning Corporation	Method of direct process performance improvement via control of silicon manufacture
DE3910665A1 (de) *	1989-04-03	1990-10-04	Bayer Ag	Verfahren zur herstellung von alkylhalogensilanen
DE3929865A1 (de) *	1989-09-08	1991-03-14	Bayer Ag	Verfahren zur herstellung von alkylhalogensilanen
US5281739A (en) *	1992-12-23	1994-01-25	Dow Corning Corporation	Process for manufacture of alkylhalosilanes
FR2707619B1 (fr) *	1993-07-01	1995-09-01	Pechiney Electrometallurgie	Silicium métallurgique contenant du phosphore et destiné à la préparation des alkyl ou aryl halogénosilanes.
NO950760L (no) *	1995-02-28	1996-08-29	Elkem Materials	Fremgangsmåte for fremstilling av alkylhalosilaner
DE19532315C1 (de) *	1995-09-01	1997-02-06	Bayer Ag	Verfahren zur Herstellung von Alkylhalogensilanen
DE19645359A1 (de) *	1996-11-04	1998-05-07	Bayer Ag	Verfahren zur Herstellung von Alkylhalogensilanen
JP3362619B2 (ja) *	1996-12-13	2003-01-07	信越化学工業株式会社	アルキルハロシランの製造方法
US6005130A (en) *	1998-09-28	1999-12-21	General Electric Company	Method for making alkylhalosilanes
US6258970B1 (en)	1999-04-19	2001-07-10	General Electric Company	Method for promoting dialkyldihalosilane formation during direct method alkylhalosilane production
US6423860B1 (en)	2000-09-05	2002-07-23	General Electric Company	Method for promoting dialkyldihalosilane formation during direct method alkylhalosilane production
FR2817546B1 (fr) *	2000-12-04	2003-01-03	Invensil	Fabrication de silicium dope par ajout de phosphore et destine a la preparation des alkyl-ou aryl-halogenosilanes
KR20110015653A (ko) *	2008-06-04	2011-02-16	다우 코닝 코포레이션	유기할로실란과 할로실란을 제조하는 개선 방법
KR101739938B1 (ko)	2009-10-16	2017-05-25	다우 코닝 코포레이션	오가노할로실란을 제조하는 방법
EP2794097B1 (fr)	2011-12-19	2017-02-08	Bluestar Silicones France	Procede de synthese directe d'alkylhalogenosilanes
KR102507061B1 (ko)	2014-12-19	2023-03-07	다우 실리콘즈 코포레이션	모노하이드로겐트라이할로실란의 제조 공정
CN112533933B (zh)	2018-09-07	2023-09-05	美国陶氏有机硅公司	用于制备烷基烷氧基硅烷的方法
WO2020050977A1 (fr)	2018-09-07	2020-03-12	Dow Silicones Corporation	Procédé de préparation d'hydrocarbylhydrocarbyloxysilanes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4520130A (en) *	1984-05-08	1985-05-28	Scm Corporation	Halosilane catalyst and process for making same
US4602101A (en) *	1985-11-12	1986-07-22	Dow Corning Corporation	Method of manufacturing alkylhalosilanes
CA1320035C (fr) *	1986-08-20	1993-07-13	William Terry Strange	Procede pour la preparation d'halosilanes

1986
- 1986-12-22 US US06/944,317 patent/US4946978A/en not_active Expired - Lifetime
1987
- 1987-11-19 CA CA000552215A patent/CA1310467C/fr not_active Expired - Lifetime
- 1987-12-12 CN CN87107397A patent/CN1014506B/zh not_active Expired
- 1987-12-15 EP EP87310994A patent/EP0273635B2/fr not_active Expired - Lifetime
- 1987-12-15 DE DE3784151T patent/DE3784151T3/de not_active Expired - Lifetime
- 1987-12-21 BR BR8706946A patent/BR8706946A/pt not_active IP Right Cessation
- 1987-12-21 AU AU82844/87A patent/AU596480B2/en not_active Expired
- 1987-12-22 JP JP62323016A patent/JP2543920B2/ja not_active Expired - Lifetime

Also Published As

Publication number	Publication date
EP0273635B1 (fr)	1993-02-10
AU8284487A (en)	1988-06-23
CN87107397A (zh)	1988-11-23
CN1014506B (zh)	1991-10-30
DE3784151T3 (de)	1998-01-22
AU596480B2 (en)	1990-05-03
US4946978A (en)	1990-08-07
EP0273635A3 (en)	1989-10-11
BR8706946A (pt)	1988-07-26
EP0273635B2 (fr)	1997-08-13
EP0273635A2 (fr)	1988-07-06
DE3784151D1 (de)	1993-03-25
JP2543920B2 (ja)	1996-10-16
JPS63166891A (ja)	1988-07-11
DE3784151T2 (de)	1993-08-26

Legal Events

Date	Code	Title	Description
2009-11-24	MKEX	Expiry

Publication	Publication Date	Title
CA1310467C (fr)	1992-11-24	Amelioration d'un procede direct au moyen du controle de la production du silicone
EP0320260B1 (fr)	1994-09-28	Méthode de préparation d'alcoylhalosilanes
EP0028009B1 (fr)	1985-05-29	Procédé pour la préparation d'une composition réactionnelle à base de silicone et catalysée par du cuivre
US4500724A (en)	1985-02-19	Method for making alkylhalosilanes
US5059343A (en)	1991-10-22	Method of direct process performance improvement via control of silicon manufacture
US4898960A (en)	1990-02-06	Method of direct process performance improvement via control of silicon manufacture
USRE33452E (en)	1990-11-20	Method for making alkylhalosilanes
JP2003531007A (ja)	2003-10-21	触体の製造方法
US6258970B1 (en)	2001-07-10	Method for promoting dialkyldihalosilane formation during direct method alkylhalosilane production
EP0411645B1 (fr)	1995-05-31	Procédé de préparation d'organohalogénosilanes
EP0893448B1 (fr)	2003-04-16	Procédé de préparation d'halogénures d'alkylsilanes
EP0436233B1 (fr)	1994-10-19	Procédé de préparation de silanes du type organohalo
EP0028057B1 (fr)	1982-11-03	Procédé de préparation de diméthylaminosilanes
US5281739A (en)	1994-01-25	Process for manufacture of alkylhalosilanes
EP0436234B1 (fr)	1996-12-11	Procédé de préparation d'organohalogénosilanes
JP2554348C (fr)	1998-12-24